Solvent-free carbonylation of glycerol with urea using metal loaded MCM-41 catalysts

Kondawar, Sharda E.; Potdar, Aparna; Rode, Chandrashekhar V.

doi:10.1039/c4ra11590b

Cited by 35 publications

(15 citation statements)

References 31 publications

(25 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The support MCM-41 was first prepared by hydrothermal method reported in the literature [30]. In a typical preparation, 2.67 g of sodium hydroxide was dissolved in 146 g of distilled water and stirred for 5 min.…”

Section: Experimental Details Catalysts Preparationmentioning

confidence: 99%

See 1 more Smart Citation

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts

et al. 2017

Self Cite

View full text Add to dashboard Cite

Glycerol carbonylation with urea is a very feasible option to produce glycerol carbonate with a net result of CO 2 fixation through urea synthesis. The prerequisite of an efficient catalyst for this reaction is to possess both acid and basic sites together. Several acidic supports were screened for ZnO catalyst in this work and Zn/MCM-41 was found to exhibit the best activity and almost complete selectivity to glycerol carbonate (GC). Although, non-catalytic glycerol carbonylation resulted in GC formation but glycerol conversion achieved was twice with Zn/MCM-41 as a catalyst. Further to that increase in Zn loading from 2 to 5% resulted in increase in glycerol conversion from 63 to 82%. The prepared catalysts were characterized by XRD, NH 3 and CO 2 -TPD and effects of reaction parameters such as catalyst loading, glycerol to urea mole ratio and temperature on glycerol conversion and GC selectivity in batch mode of operation were also studied. Time on stream activity of 5% Zn/MCM-41 catalyst for continuous carbonylation of glycerol was also studied for *100 h with an average conversion of *55% and complete selectivity to GC. This indicated five times lower productivity of GC per h due to lower residence time than that in a batch operation as compared to that of a continuous operation. Activation energy estimated from the Arrhenius plot was found to be 39.82 kJ mol -1 suggesting that the reaction is kinetically controlled. A reaction pathway mediated by acid and basic sites of the Zn/MCM-41 catalyst is also proposed.

show abstract

Section: Experimental Details Catalysts Preparationmentioning

confidence: 99%

“…Recently, we have reported screening study of various MCM-41 supported Cu, Ni and Zn oxide catalysts for glycerol carbonylation with urea to give GC [30]. In continuation, we studied in detail the role of different supports and loading of Zn in glycerol-urea reaction to produce GC.…”

Section: Introductionmentioning

confidence: 99%

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…For example; the two different metal cations can be represented as M A n + and M B n + in polyhedra, which connect in various possible ways such as edge‐ or corner‐sharing M A –O–M B –O, M A –O–M A –O or M B –O–M B –O metal–oxygen chains. This gives different cation environments leading to different active centers and different reactivity towards an approaching molecule …”

Section: Introductionmentioning

confidence: 99%

“…Sn-W mixed metal oxides, [10] La 2 O 3 , [11] Co 3 O 4 /ZnO, [12] Au/ Fe 2 O 3 , [13] Sm 0.6 TPA, [14] Zn 1 TPA, [15] ZnSn(OH) 6 , [16] Zn-exchanged zeolites, [17] Zn/MCM-41, [18] and quaternary ammonium ion exchanged montmorillonite. [19] Among them, the zinc based catalysts have shown ap romising activity because of their Lewis acidic nature.…”

Section: Introductionmentioning

confidence: 99%

“…This gives different cation environments leadingt od ifferent active centers andd ifferent reactivity towards an approaching molecule. [18,[20][21][22] Herein, we report the bifunctional Zn-Sn composite oxide catalystf or the eco-friendly synthesiso fg lycerol carbonate from glycerolw ith urea. The influence of catalyst preparation methods towards its catalytic activity was systematically studied by three different routes, namely,c oprecipitation,s olidstate ande vaporation methods.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Novel Bifunctional Zn–Sn Composite Oxide Catalyst for the Selective Synthesis of Glycerol Carbonate by Carbonylation of Glycerol with Urea

2015

View full text Add to dashboard Cite

A novel Zn–Sn composite oxide is reported as a solid bifunctional catalyst for glycerol carbonylation to give glycerol carbonate in high yields. It was prepared by coprecipitation, solid‐state and evaporation methods. Physico‐chemical properties of the catalysts were investigated by XRD, N2 sorption, temperature‐programmed desorption, SEM, and TEM techniques. Coprecipitation was found to be better than the other two methods for carbonylation of glycerol. Higher activity of the catalyst was attributed to a high amount of active sites. A series of Zn–Sn composite oxides with different metal contents and effect of calcination on glycerol carbonate synthesis were also studied. The correlation of activity with total active sites of the catalyst was obtained. Zn–Sn composite catalyst with Zn/Sn molar ratio=2:1 calcined at 600 °C exhibited 96.0 % glycerol conversion with 99.6 % selectivity towards glycerol carbonate under optimized reaction conditions. The catalyst was recycled four times with a marginal decrease in activity.

show abstract

Bifunctional molybdenum phosphate catalyst with tunable acidity–basicity for the sustainable synthesis of glycerol carbonate via solvent‐free carbonylation of glycerol with urea

Bhaduri

Auroux

Bhaumik

et al. 2022

Applied Organom Chemis

View full text Add to dashboard Cite

Tuning the surface acidity–basicity via molecular level control of the chemical composition of the catalyst is one of the thrust areas of research. Herein, we first report a bifunctional molybdenum phosphate catalyst with tunable acidity–basicity for the sustainable synthesis of glycerol carbonate involving glycerol and urea. The catalyst has been thoroughly characterized by using powder X‐ray diffraction, Fourier‐transform infrared, X‐ray photoelectron spectroscopy, N2 physisorption, field emission scanning electron microscopy, transmission electron microscopy, temperature programmed desorption (TPD), Py‐IR, 31P nuclear magnetic resonance and thermogravimetric analysis. It has been observed that the physicochemical properties of the catalysts changed considerably by varying the metal and phosphorus concentrations. The molybdenum phosphate catalyst with Mo/P molar ratio = 1:3 was found most active, having the highest acidity to basicity ratio. Interestingly, the reason could be associated to the presence of higher Brønsted acidity, as evidenced from the TPD and Py‐IR results. The physicochemical properties of the used catalyst suggest it as a stable and reusable catalyst. A study on operating parameters was carried out to optimize catalytic performance to obtain glycerol conversion up to 95% at a glycerol carbonate selectivity of 99%. This remarkable catalytic performance could be attributed to the bifunctional nature of the catalyst.

show abstract

Solvent-free carbonylation of glycerol with urea using metal loaded MCM-41 catalysts

Abstract: Reacting glycerol with urea is the most attractive option for the production of glycerol carbonate (GC), as it utilizes two inexpensive chemicals readily available in the chemical cycle.

Cited by 35 publications

References 31 publications

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts

Novel Bifunctional Zn–Sn Composite Oxide Catalyst for the Selective Synthesis of Glycerol Carbonate by Carbonylation of Glycerol with Urea

Bifunctional molybdenum phosphate catalyst with tunable acidity–basicity for the sustainable synthesis of glycerol carbonate via solvent‐free carbonylation of glycerol with urea

Contact Info

Product

Resources

About